DD274557A5 - FUNGICIDAL AGENTS - Google Patents

Abstract

The invention relates to fungicidal compositions containing a solid or liquid Traegerstoff and an ortho-substituted carboxylic acid benzyl ester of the formula in which R 1 alkoxy, alkylthio, halogen or amino, R 2 alkoxycarbonyl, cyano or CONH 2, R 3 is hydrogen, halogen, cyano, aryl, Aryloxy, a saturated or unsaturated heterocyclic radical, cycloalkyl or substituted cyclopropyl, X is alkylene or n is 0 or 1, and methods for the preparation of the fungicidal agents, the use of the active compounds as fungicides and methods for controlling fungi with these active ingredients. It is known to use N-tridecyl-2,6-dimethylmorpholine or a- (2-benzoyloxyphenyl) b-methoxy-acrylic acid methyl ester as fungicides (DE 1 164 152, EP-178 826). However, their fungicidal effects are insufficient in some cases. The aim of the invention is the development of fungicidal agents with improved efficacy in fungi, but crops are not damaged. formula

Description

The new fungicides can be used in agriculture as fungicides.

Characteristic of the known technical solutions

It is known to use N-tridecyl-2,6-dimethylmorpholine or "- {2-benzoyloxyphenyl) / 3-methoxyacrylic acid methyl ester as fungicides (OE 1) 64,152, EP-178 826). However, their fungicidal effects are in some cases insufficient.

Object of the invention

The aim of the invention is the development of fungicidal agents with improved efficacy in fungi, but crops are not damaged.

Explanation of the essence of the invention

The invention has for its object to provide new chemical compounds with fungicidal activity.

It has been found that new ortho-substituted carboxylic acid benzyl esters of the formula

R ³ - (X) -CO-CH ₂ η

R 2

in which R ^{1 is} C ₁ -C 4 -alkoxy, C ₁ -C 18 -alkylthio, halogen or, if appropriate, C ₁ -C 4 -alkyl, mono- or di-unsubstituted amino,

'R ^{2 is} Ci-Cij-alkoxycarbonyl, cyano or the group CONH ₂ ,

R ^{3 is} hydrogen, halogen, cyano, aryl. Aryloxy, wherein the aromatic ring is optionally substituted by one or more of the following radicals: C ₁ -C ₆ -AUyI. C ₂ -C ₁ -alkenyl, C ₁ -C ₂ -haloalkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl, aryl, aryl-C ₁ -C ₄ -alkyl, aryloxy, aryloxy- -Ci, -alkyl, aryloxy - ^ - C ^ alkoxy, haloaryloxy-C ^ C ^ alkoxy, halogen, halo-C ^ C ^ alkoxy. C ₁ -C -alkylthio, thiocyanato. Cyano, nitro, or R ^{3 is} a saturated or unsaturated heterocyclic radical, C3-C7-cycloalkyl, Cs-Cβ-cycloalkenyl, adamantyl, fluorenyl or a substituted cyclopropyl radical which is substituted by methyl, halogen

(Chlorine, bromine), C 1 -C 4 -haloalkyl (trifluoromethyl, tetrabromethyl, oichloro-dibromoethyl), C ₃ -C 1 -alkenyl (methylvinyl, oimethylvinyl), C ₂ -C 1 -haloalkenyl (dichlorovinyl, oichlorobutadienyl, difluorovinyl, trifluoromethyl-vinyl) , Methoxycarbonyl-CaCl-alkenyl (methylmethoxycarbonylvinyl), cyclopentylidenemethyl, phenyl, halophenyl (chlorophenyl), C ₁ -C ₂ -alkoxyphenyl (ethoxyphenyl), C ₁ -C ₄ -alkylphenyl (tert-butylphenyl),

X is a straight-chain or branched, optionally substituted by halogen or hydroxy, optionally also unsaturated CfCi ₂ alkylene radical and

η the numbers O or 1 means have an excellent fungicidal activity.

15 The radicals listed in the formula may have the following meanings, for example:

R ¹ may, for. B. optionally branched Ci ~ Ci, alkoxy (eg., Methoxy, ethoxy, n- or iso-propoxy, n-, iso-, see- or tert-butoxy), Ci-Ci.-Alkylthio (z. Methylthio, ethylthio, n- or iso-propylthio, η-, iso-, 'see- or tert-butylthio), halogen (for example chlorine, bromine), if appropriate by C 1 -C 4 -alkyl, monosubstituted or substituted (eg, amino, methylamino, methylethylamino, dimethylamines, diethylamino, diisopropylamino).

R ² may, for. B. Ci-C ^ alkoxycarbonyl (eg., Methoxycarbonyl, ethoxycarbonyl, n- or iso-propoxycarbonyl, n-, iso-, see- or tert-butoxycarbonyl), cyano or the group CONH ₂ be.

R ³ may, for. B. hydrogen, halogen (eg., Fluorine, chlorine, bromine), cyano, aryl (phenyl, naphthyl) or aryloxy (phenyloxy), wherein the aromatic ring may optionally be substituted by one or more of the following radicals: C 6 -alkyl (for example methyl, ethyl, η or iso-propyl, n-, iso-, he- or tert-butyl, η-, iso-, hepta-, tert-or neopentyl, hexyl), C ₂ -C, alkenyl (e.g., vinyl, allyl), Ci-C ₂ haloalkyl (eg. B. Üifluormethyl, trifluoromethyl), Ci-C6-alkoxy (e.g., 3, methoxy, ethoxy, iso-propoxy, tert-butoxy), Ci-C ^ - 'alkoxy-Ci-Cij-alkyl (eg., Methoxymethyl), aryl (ζ.Phenyl), aryl-Ci-C ₂ -alkyl (ζ Benzyl). Aryloxy (ζB. phenoxy), aryloxyCi-C ^ -alkyl (ζB. phenoxymethyl, phenoxyethyl), aryloxy-Ci-Cij-alkoxy, haloaryloxy-Ci-C ^ alkoxy, (eg Phenoxymethoxy , Phenoxyethoxy, phenoxypropoxy, 2-chloro-phenoxy-ethoxy, 4-chloro-phenoxyethoxy), halogen (eg fluorine, chlorine, bromine, iodine), halogeno-C 1 -C 4 -alkoxy (ζB 1, 1, 2, 2-tetrafluoroethoxy), Ci-Ci, -Alkylthio (ζ B. B. Methylthio). Thiocyanato, cyano. Nitro.

274SS7

R ³ may further represent a saturated or unsaturated heterocyclic radical (eg, furyl, pyrrolyl), Ca-Cy-cycloalkyl. C ₅ -C ₆ cycloalkenyl. (eg cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl), 1-adamantyl, 9-fluorenyl or a substituted cyclopropyl radical which is substituted by methyl, halogen (chlorine, bromine), Ci-C ₂ - Haloalkyl (trifluoromethyl, tetrabromethyl, dichloro-dibromoethyl), Ca-Cif-alkenyl (methylvinyl, dimethylvinyl), Ca-Cij-haloalkenyl (oichlorovinyl, dichlorobutadienyl, difluorovinyl, trifluoromethylvinyl), methoxycarbonyl-CaCl-alkenyl (methyl-M'-) -hoxy-

10 carbonylvinyl), cyclopentylidenemethyl, phenyl, halophenyl

(e.g., fluorophenyl, chlorophenyl, bromophenyl, dichlorophenyl), Ci-C2-alkoxyphenyl (e.g., methoxyphenyl, ethoxyphenyl), Ci-Ci, -alkylphenyl (e.g., methylphenyl, ethylphenyl, butylphenyl, t-butylphenyl), such as:

2,2-Dimethy1-3- (2 ', 2'-dimethylvinyl) cyclopropyl (A1)

2,2-Dimethyl-3- (2 ', 2 ¹ -dichlorovinyl) -cyclopropyl (A2)

2,2-Dimethyl-3- (2 ¹ , 2'-dibromovinyl-cyclopropyl (A3)

2,2-Dimethyl-3- (2'-trifluoromethyl-2'-chlorovinyl) -cyclopropyl (A4)

2,2-dichloro-3,3-dimethylcyclopropyl (A5)

2,2,3 ', 3-tetramethylcyclopropyl (A6)

2,2-Dimethyl-3- (2 ', 2'-difluorovinyl) -cyclopropyl (A7)

2,2-0imethyl-3- (2-trifluoromethyl-2 * ¹ fluorovinyl) -cyclopropyl (A8) 2, 2-Dimethy 1-3- (?. '-Methyl-2' -methoxycarbonylvinyU-cyclo-propyl (A9)

2,2-dimethyl-3-U ', 4'-dichlorobutadienyl) -cyclopropyl (A10)

2,2-Dimethyl-3- (r-bromo-2 ', 2', 2'-tribromoethyl) -cyclopropyl (A11) 2,2-dimethyl-3- (1'-bromo-2 ', 2'-dichloro -2'-bromoethyl) -cyclopropyl (A12) 2,2-Dimethy1-3-cyclopentylidenemethyl-cyclopropyl (Λ13)

1- (4 ¹ -Ethoxyphenyl) -2,2-dichloro-cyclopropyl (A14)

2,2-Dimethyl-3- (4'-tert-butylphenyl) cyclopropyl (A15)

The radical X listed in the general formula I can mean, for example:

a straight-chain C 1 -C 4 -alkylene radical (for example methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene), a branched C 1 -C 12 -alkylene radical (for example methylmethylene, dimethylinethylene, ethylmethylene, n- or iso Propylmethylene, methylethylene, methylpropylene, dimethylpropylene, ethylpropylene, methylbutylene, dimethylbutylene, ethylbutylene, n- or iso-propylbutylene, methylpentylene, dimethylpentylene, trimethylpentylene, methylhexylene, dimethylhexylene, trimethylhexylene, ethylhexylene, n- or iso-propylhexylene, methylheptylene). a C 2 -C 6 alkenylene radical (for example, vinylene, allylene, methylallylene, butenylene, methylbutenylene), a C 1 -C 4 -alkylene radical substituted by halogen (for example chloromethylene, dichloroethylene,

Fluoromethylene, difluoroethylene, bromomethylene, oibromoethylene, chloroethylene, fluoroethylene, bromoethylene, fluoropropylene, chloropropylene, bromopropylene, fluorobutylene, chlorobutylene, bromobutylene), a halo-substituted C2-Ci, alkenylene radical (eg, chlorovinylene, oichlorvinylene), one by hydroxy substituted Ci-Ca-alkyl radical (eg hydroxymethylene, hydroxyethylene).

X _n means a single bond for the case η = 0. The new compounds may e.g. be prepared by one

ortho-substituted benzyl bromide of the general formula III, in which R ¹ and R ^{2 have} the abovementioned meaning, with an alkali, alkaline earth or ammonium salt of a carboxylic acid of the formula II, wherein R ³ , X and η have the abovementioned meaning, in one Solvent or diluent and optionally with the addition of a catalyst to the new compounds.

R ³ - (X) -CO-SaIz

II

+ Br-CH ₂ - ^

III

R 3 - (X) -CO-CH ₂ -C ^v

The preparation of carboxylic acid esters from Alkylhalogeni.Jcn and 2Q carboxylates is known per se (see, for example, Synthesis 1975, 805).

Suitable solvents or diluents for the reaction of II with III are acetone, acetonitrile, dimethyl sulfoxide, oioxane, dimethylformamide, N-methylpyrrolidone, N ₁ N * -dimethylpropyleneurea, or pyridine.

25

In addition, it may be advantageous to the reaction mixture, a catalyst such. As tetramethylethylenediamine, in an amount of 0.01 to 10 Z (wt. I), based on compound III, to add.

274SS7

The carboxylic acids used are either known or can be prepared by methods analogous to known methods. Corresponding production methods are e.g. described in: Chem. Ber. 119 (1986) 3694; Synthesis 1987, 738; Angew. Chem. 93 (1981) 719.

The preparation of the ortho-substituted benzyl bromides of the general formula III can be carried out, for example, by bromination of ortho-substituted toluene of the general formula IV with N-bromosuccinimide (A.ngew Chem. Ν (1959) 349).

"- {2-Bromomethylphenyl) acrylic esters of the general formula III (R ¹ = alkoxy, R ² = alkoxycarbonyl) are known from OE-35 19 280, OE-35 45 318 and DE-35 45 319.

IV

Because of their C =C double bond, the compounds of general formula IV can be present both as E and Z isomers. The isomers may e.g. be separated by chromatography, fractional crystallization or distillation in the usual manner. The invention encompasses both the individual isomeric compounds and their mixtures.

The compounds of the general formula IVa (R ¹ = alkoxy, R ² = alkoxycarbonyl, cyano) are obtained from the hydroxymethylene derivatives of the general formula V ₁ which may be in equilibrium with the formyl derivatives VI, with an alkylating agent (eg dimethylsulfate) in Presence of a base (eg potassium carbonate) in a diluent (eg acetone). In the following formulas, "alk" represents a Ci-C ^ alkyl group and X is a leaving group (eg, methyl sulfate).

H ₃ C

R ²

VI

R ²

VI

VI

VI

X-Alk / Base

K ₃ C

R 2 CH.

IVa

R ² = alkoxycarbonyl, cyano

For the preparation of the compounds of the general formula IVb (R '= alkylthio, R ² = alkoxycaruonyl, cyano), the hydroxymethylene derivatives V. which can also be present in equilibrium with VI, first with sulfonic acid chlorides, such as. For example, methanesulfonyl chloride (R '= methyl), trifluoromethanesulfochloride (R' = trifluoromethyl) or p-toluenesulfonyl chloride (R '= p-methylphenyl), in the presence of bases (eg triethylamine) to the compounds of the general formula VII implemented. Subsequently, the desired compounds IV b are obtained by reacting VII with alkyl thiols of AlCO 2, such as, for example, sodium thiomethylate.

Cl-SO ₂ -R '

-> H ₃ C

Alk Sun

OSO ₂ R '

-> H ₃ C

^ Saik

IVb R ² = alkoxycarbonyl, cyano

Compounds of the general formula IVc (R '^ halogen, R ² = alkoxycarbonyl, cyano) are obtained by reacting the hydroxymethylene compounds V, which may be in equilibrium with the formyl derivatives VI, with inorganic acid chlorides (eg phosphorus pentachloride) ( See, for example, Chem. Ber, H (1918) 1366).

PCl ₅

> H ₃ C

IVc R ² = alkoxycarbonyl, cyano

2745S7

The preparation of the compounds of the general formula IV d (R '= alkylamino or dialkylamino, R ² = alkoxycarbonyl, cyano) is carried out by reacting the hydroxymethylene derivatives V. which may also be present in equilibrium with VI, with primary or secondary amines. Alternatively, the alkali salts of V can also be reacted with the hydrochlorides of primary or secondary amines with the liberation of sodium chloride (see Ann. Chim. [10] H (1932) 103).

HNAIk ₂

-> H ₃ C

NAIk ₂

IVd

I? ² = alkoxycarbonyl, cyano

Compounds of the formula IVd are also obtained by reacting methyl 2-methylphenylacetate VIII or 2-methylphenyl-acetonitrile IX with oialkylformamide dialkyl acetals or with aminalkyl esters (cf., for example, Chem. Ber. 97 (1964). 3396)

(AIkO) ₂ CH-N (Mk) ₂

> K ₃ C

VIII: R ² = alkoxycarbonyl IX: R ² = cyano

IVd

The new compounds of formula I where R ² = C0NH ₂ are obtained starting from the corresponding derivatives with R ² = cyano by alkaline saponification (compare Synthesis 1980, 243).

ⁿ ie required as starting compounds Hydroxymethylenderivate of the general formula V ₁ in the R ² alkoxycarbonyl rder cyano, obtained from 2-methylphenyl acetic acid alkyl esters VIII or from 2-methylphenylacetonitrile IX by reaction with ants _f säuremethylester using a base (eg. B Sodium hydride) in an inert solvent such. B diethyl ether or tetrahydrofuran (see Ann. Chem. 424 (1921) 214).

AusfOhrungsbeispiele

, 30 The following example! ^ Are intended to explain the preparation of the new active ingredients.

example 1

'- (2-Benzoyloxymethylphenyl) - / - methoxyacrylate

C-O-CH2

C = CH-OCH ₃

12.2 g (0.1 mol) of benzoic acid and 5, B g (0.1 mol) of potassium hydroxide are dissolved in 150 ml of ethanol and stirred for two hours at room temperature (20 ⁰ C). Oe precipitated, white precipitate is filtered off, washed with diethyl ether and suspended in 300 ml of dimethylformamide. Subsequently, 28.5 g (0.1 mol) of alpha- (Z Bromomethylphenyl) - /? - Methoxyacrylsäuremethylester be added. The mixture is stirred for 24 hours at room temperature, then the reaction mixture is concentrated and the residue is taken up in methylene chloride. The organic phase is washed with water, dried over MgSO 4, and concentrated. The resulting oil is chromatographed on silica gel (cyclohexane: ethyl acetate 10: D ) to give 25.4 g (78 l) of the title compound as a colorless, viscous oil (Compound No. 83).

Example 2

a- [ 2- (1'-ortho-chlorophenyl) -cyclopropylearbonyloxymethylphenyl] - / 9-methoxy-acrylic acid methyl ester

Cl

1 V7

OCH ₃

a) A mixture of 30, 'g (200 mmol) of 2-qnlorbenzylcyanid and 80.0 g (426 mmol) of dibromoethane are slowly added dropwise to a solution of 40.0 g of triethylbutylammonium chloride in 200 ml of sodium hydroxide solution (30' /.ig). The mixture is stirred for 2 hours at 80 ⁰ C, allowed to cool, hydrolyzed with 500 ml of ice water and extracted with DJ - »thylether. The organic phase is washed with ammonium chloride solution and water, dried over MgSO 4, and concentrated. The resulting oil is purified by distillation (97 ⁰ C, 0.4 mbar). This gives 20.0 g (56 Z) of 1 - (2 * -ChlorphenyU-cyclopropylnitrile as a colorless liquid.

74SS7

b) 11.0 g (62 mmol) of 1- (2'-chlorophenyl) -cyclopropylnitrile and 10.0 g (180 mmol) of potassium hydroxide are refluxed in 130 ml of diethylene glycol for two hours. It is allowed to cool, hydrolyzed with 200 ml of water and extracted with diethyl ether. The aqueous phase is acidified with HCl (dil.) And extracted with methylene chloride. The combined methylene chloride phases are dried over MgSO 4, dried, concentrated and covered with hexane. By grinding to obtain 9.9 g (81 Z) of 1- (2-chlorophenyl ¹⁾ -cyclopropancarbonsauro in the form of colorless crystals (mp .: 160 ⁰ C).

10

c) 9.8 g (50 mmol) of 1- (2-chlorophenyl ¹⁾ -cyclopropancarbonsaure and 2.8 g (50 mmol) of potassium hydroxide are dissolved in 100 ml of ethanol for one hour at room temperature (20 ⁰ C) stirred. The precipitated, white precipitate is filtered off, washed with diethyl ether and suspended in 300 ml of N-methylpyrrolidone. Subsequently, H.3 g (50 mmol) of <x- (2-bromomethylphenyl) - / 9-methoxyacrylic acid methyl ester are added. The mixture is stirred for two hours at 70 ⁰ C, allowed to cool, hydrolyzed with 150 ml of water and extracted with methyl tert-butyl ether. The organic phase is washed with water, dried over MgSO 4, and concentrated.

The resulting oil is overcoated with hexane and triturated

crystallized. This gives 12.8 g (64 7) of the title compound as white crystals (m.p .: 100-101 ⁰ C).

The following compounds can be prepared in a corresponding manner: 25

30 35 AO

R ³ - (X) -CO-CH ₂ -C ⁷ η H ₃ CO

"OCH ₃

Table 1: Compounds of the formula I (R ¹ = OCH ₃ R ₂ = CO ₂ CH ₃ ) The configuration information relates to the / 8-methoxy-acrylic ester group

No. R ³

H

(X) ₁

-CH ₂ -

configuration

2 H -CH ₂ -CH ₂ - e 3 H -CH ₂ -CH (CH ₃ ) - e ; H -CH ₂ -C (CH ₃ I ₂ - e 5 H -CH = CH- e 6 H -CH = C (CH ₃ ) - ' e 7 H -CSC- e θ H -CH ₂ -CH ₂ -CH ₂ - e 9 H -CH ₂ -CH ₂ -CH (CHa) - e 10 H -CH ₂ -CH (CH 3) -CH ₂ - e 11 H -CH ₂ -CH ₂ -C (CH 3) 2- e 12 H -CH ₂ -C (CH 3) 2 -CH ₂ - e 13 H - I ₂ -CH ₂ -C (C ₂ H ₅ I ₂ - e H H -CH = CH-CH ₂ - e 15 H -CH ₂ -CH = CH- e 16 H -CH ₂ -C (CH ₃ J = CH- e 17 H -CH ₂ -CH = C (CH ₃ ) - e 18 H - (CH ₂ ) _; _ e 19 H -CH ₂ -CH ₂ -CH ₂ -CH (CH ₃ ) - e

¹ H NMR data (CDd ₃ ), δ in [ppm]

2:05 (S.3H); 3.69 (s.3H); 3.80 (s, 3H); 5.02 (s, 2K) 7.35 (m.AH); 7:57 (s, 1H).

Mp ( ⁰ C)

Oei

74 -

61 OeI

Oei

Γ. k> (X) _n configuration e 20 H -CH ₂ -CH (CH ₃ I-CH ₂ -CH ₂ - e 21 H - (CH ₂ J ₃ -C (CH ₃ J ₂ - e 22 H - (CH ₂ J ₃ -CH (C ₂ H ₅ ) - e 23 H - (CH ₂ J ₃ -CH (OC ₃ H ₇ ) - e 2; η ' -CH ₂ -CH = CH-CH ₂ - e 25 H -CH ₂ -C (CH ₃ J = CH-CH ₂ - e 26 H - (CH ₂ J ₅ - e 27 H - (CH ₂ J ₄ -CH (CH ₃ ) - e 28 H - (CH ₂ J ₄ -CH (C ₂ H ₅ ) - e 29 H - (CH ₂ J ₃ -CH (CH ₃ J-CH ₂ - e 30 H -CH ₂ -CH = CH-CH = CH- e 31 H -CH ₂ -C (CH ₃ J = CH-CH = CH- e 32 H - (CH ₂ J ₆ . e 33 H - (CH ₂ ) S-CH (CH ₃ ) - e 3; H - (CH ₂ J ₄ -CH (CH ₃ J-CH ₂ -

¹ H-NMR

Mp ( ⁰ C)

35 H - (CH ₂ ) ₅ -CH (nC ₃ H 7) - E

36 H - (CH ₂ J ₇ -

37 H - (CH ₂ ) 6 -CH (CH 3) - E

38 H - (CH ₂ ) ₅ -CH (CH ₃ ) -CH ₂ -E

39 H -t ^CH 2) ₆ -C (CH 3) 2 -E

o η - (CH ₂ J ₈ .E

41 H - (CH ₂ J ₉ - E

42 H -ICH ₂ J ₁₀ - E

43 H-CHCl-E

Oei

Oei

0.83 (t.3H); 0.93 (d, 3H); 1.29 (m, 4H); 1.96 (m, 1H);

2.33 (m.1H);

3.79 (s, 3H);

OeI OeI

2,131m.1H); 3.69 (s, 3H); 5, 03 (s, 2H); 7,571s, 1H).

7.32 (m, 4H);

Oei

H -CCl ₂ - configuration 44 Cl -CCl ₂ - e 45 H -CHBr- e 46 H -CBr ₂ e 47 br -CBr ₂ - e ; β H --CHF-- e 49 H -CF ₂ - e 50 F -CF ₂ - e 51 H -CH = CCl- e 5? H --CCl = CCl e 53 Cl -C (CH ₃ J ₂ - e 54 br -C (CH ₃ I ₂ - e 55 H -CHCl-CH (CH ₃ ) - e 56 H -CHCl-C (CH ₃ I ₂ - e 57 H -CHBr-CH (CH ₃ ). e 58 br C (C ₂ H5) 2- e 59 H -CH (OH) - e 60 H -CH ₂ -CH (OH) - e 61 H -CH ₂ -CH ₂ -CH (OH) - e 62 H -CH ₂ -CH (0H) -CH ₂ - e 63 H -CH (OH) -CH ₂ . e 64 H -CH (OH) -C (CH ₃ J ₂ - e 65 H -CH ₂ -C (OH) (CH 3) - e 66 H -CH ₂ -CH (CH ₃ J-CH (OH) e 67 H -CH = CH-CH (OH) - e 68 H -CH = CH-CH ₂ -CH (OH) - e 69 CN -CH ₂ - e 70 cyclopropyl - e 71 cyclobutyl - e 72 e

¹ H-NMR

Mp ( ⁰ C)

Oei

73 cyclopentyl - 74 cyclohexyl - 75 adamantyl - 76 9-fluorenyl - 77 cyclopentyl -CH ₂ - 78 3-cyclopentenyl -CH ₂ - 79 cyclohexyl -CK ₂ - 80 cyclopentyl -CH ₂ -CH ₂ 81 cyclohexyl -CH ₂ -CH ₂ 82 cyclohexyl - (CH ₂ J ₃ - 83 C ₆ H ₅ (= phenyl) 84 2-CH ₃ -C 6 H 4 85 3-CH ₃ -c ₆ H ₄ - 86 4-CH ₃ -C ₆ H ₄ - 87 2.3- (CH ₃ J ₂ -C ₆ H ₃ - 88 2.4- (CH ₃ J ₂ -C ₆ H ₃ - 89 2.6- (CH ₃ J ₂ -C ₆ H ₃ - 90 3.4-JCH ₃ J ₂ -C ₆ H ₃ _ 91 3.5- (CH ₃ I ₂ -CcH ₃ - 92 2,4.6- (CH _{3) 3} -C6H2 - 93 4-t C; H ₉ -C ₆ H; - 94 2-C ₆ H ₅ -C ₆ H ₄ - 95 4-C ₆ H ₅ -C ₆ H - 96 2-benzyl-C _6Hi , - 97 4-benzyl-C ₆ H .; -

configuration

E N G E R E S E S E

EE E E E

E E

E E

¹ H-NMR

Mp ( ⁰ C) OeI

3.60 (s, 3H); 3.76 (s.3H); 5.27 (s, 3H); 7.50 (m, 9H); 7:57 (s.1H).

Oei

OeI OeI OeI

No. RJ 96 2-Cl-C ₆ H ₄ 99 3-Cl-C ₆ H ₄ ΐ OO 4-Cl-C ₆ H ₄ 101 2,4-Cl ₂ -C ₆ H ₃ 10? 2.5-Cl ₂ -C ₆ H ₃ 103 2.6-Cl ₂ -C ₆ H ₃ 104 3.4-Cl ₂ -C ₆ H ₃ 105 3.5-Cl ₂ -C ₆ H ₃ 106 2.4.5-Cl ₃ -C ₆ H ₂ 107 2,3,4,5,6-Cl ₅ -C ₆ 108 2-F-4-Cl-C ₆ H ₃ 109 2-FC ₆ H ₄ 110 3 "FC ₆ H ₄ 111 * -FC ₆ H ₄ 112 2.4-F ₂ _c ₆ H ₃ 113 2.6-F ₂ -C ₆ H ₃ 114 2,3,4,5,6-F ₅ -C ₆ 115 2 "CF ₃ -C ₆ H ₄ 116 3-CF ₃ -C 6 H ₄ 117 4-CF ₃ -C 6 H 4 118 2-0CH ₃ -C ₆ H ₄ 119 3-0CH ₃ -C ₆ H ₄ 120 4-OCH ₃ -C ₆ H ₄ 121 2-phenoxy-C ₆ H ₄ 122 3-phenoxy-C ₆ H ₄ 123 4-phenoxy-C _6H ,

(X) _n configuration

E E E

EE E R E S E

EE E E

EE E R E S E

¹ H-NMR

3.65 (s.3H); 3.83 (s.3H); 5.30 (5.2H); 7:55 (m, 8H); 7.63U.1H).

3.62 (s.3H); 3.73 (s, 3H); 5.27 (s, 2H); 7.48 (m, 7H); 7.68 (s, 1H).

Mp ( ⁰ C) OeI

Oei

3.63 (s, 3Hi, 3.73 (s, 3H), 5.29 (s.2H), 7.49 (m, 8H), 7.60 (s.1H);

68 -

68 -

Oei

63 -

Oei

Oi "Si

124 125 126 127 ί 26 129 130

136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151

(X) ₁

4-ethoxy-C ₆ H ₄ 2-phenoxyethoxy-C ₆ H ₄

2- (2 * -Cl-phenoxyethoxyJ-C ₆ H ₄

2- (3'-Cl-Phenoxyethoxy-C ₆ H ₄

2-U'-Cl-Phenoxyethoxy JC ₆ H ₄

3-phenoxyethoxy-C ₆ H;

3- (4'-C ₁ -phenoxyethoxy-4-phenoxyethoxy-C ₆ H;

2-phenoxypropoxy-C ₆ H ₄ 3-phenoxypropoxy-C ₆ H; 4-phenoxypropoxy-C ₆ H;

2-CH3-C 6 H *

4-phenyl-C _6Hit

2-FC ₆ H ₄ 3-FC ₆ H ₄

2-Cl-C ₆ H ₄ 3-Cl-C ₆ H ₄ 4-Cl-C ₆ H ₄

2,4-Cl ₂ -C 6 H 3

2,6-Cl ₂ -C ₆ H ₃ 2-Cl-4-FC ₆ H ₃ 2-ethoxy-C ₆ H ₄

4-thoxy-C _{6H (} , 2-0CH ₃ -C ₆ H _{4 4} -OCH ₃ -C ₆ H ₄

-CH ₂ -

-CH ₂ -

-CHCH3-

-CH ₂ -

-CH ₂ -

-CH ₂ -

-CH ₂ -

-CH2-

-CH2-

-CH ₂ -

-CH2-

-CH ₂ -

-CH ₂ -

-CH ₂ -

-CH2- -CH2- -CH ₂ -

configuration

E E

E N G E R E S E

E N G E R E S E S E

E E E

¹ H-NMR

Mp ( ⁰ C)

3.59 (s, 2H); 3.63 (s.3H); 3.65 (s.3H); 7.28 (m.9H); 7.52 (s.1H).

Oei

(X) _n

configuration

¹ H-NMR

Mp ( ⁰ C)

4-tC; Hg-C ₆ H;

C ₆ H ₅

4-Cl-C ₆ H;

155 4-FC ₆ H; 156 4-0CF ₂ HC ₆ H; 157 ^C 6H ₅ 158 2-0CH ₃ -C ₆ H; 159 3-0CH ₃ -C ₅ H; 160 4-OCH ₃ -C ₆ H; 161 4-Cl-C ₆ K; 162 ^C 6H ₅ 163 CeH ₅ 164 ^C 6H ₅ 165 ^C 6H ₅ 166 C ₆ H ₅ 167 C6H ₅ 168 4-tC; _H g_ _C g _H 169 '.-iC; H ₉ -C ₆ H 170 2-Cl-C ₆ H; 171 3-Cl-C ₆ H; 172 4-Cl-C ₆ H;

-CH ₂ - ε

-CHIiSO-C ₃ H ₇ ) - ε

-CH (iso-C ₃ H 7) - E

CHdSO-C ₃ H ₇ ) - e CHIiSO ₃ -C ₃ H ₇ ) - ε CH (OH) - ε CH (OH) - ε CH (OH) - ε CH (OH) - e CH (OH) - ε CHICH20H) - ε CH2-CH2 ε CH (CH3) -CH2- ε CH ₂ -CH (CH ₃ ) - e CH (CH ₃ ) -CH (CH ₃ ) - ε CH (C 6 H ₅₎ -CH 2 ε CH2-CH2 ε CH2-CH (CH3) - ε CK ₂ -CH2- ε CH2-CH2 e CH2-CH2 ε

0.75 (C, 3H); 1:07 (d.3H); 2:33 (m, IH); 3.22 (d, 1H); 2.73 (s, 3H); 3.83 (s, 3H); 5.03 (dd, 2H); 7.35 (m, 8H); 7.58 (s.1H).

Oei

Oei

Oei

3.12 (d.2H); 3.72 (s, 3H); 3.83 (s.3H);

4.62 (t.1H); 4.99 (s, 2H); 7.3Km.14H); 7.60 (s.1H).

1.16 (d.3H); 1.3O (s, 9H); 2.72 (m, 2H);

3.02 (m.1H); 3.70 (s, 3H); 3.82 (s, 3H);

5.00 (s.2H); 7.18 (m.8H); 7.60) s, 1H).

Oei

Oei

(X) ₁

configuration

Ih-NMR

Mp ( ⁰ C)

163 184 185 186 187 188 189 190 191 192 193 194 195 1S6 197 198 199

1-FC ₆ H ₄ 2-0CH ₃ -

2-Cl-C ₆ H ₄

3-Cl-C ₆ H ₄

2.6-Cl ₂ -C ₆ H ₃ 2.4-Cl ₂ C ₆ H ₃ 2-FC ₆ H ₄

2 "CF ₃ -C ₆ H ₄ ^ -CF ₃ -C ₆ H; 2" CH ₃ -C ₆ H ₄

4-tC ₄ Hg-C ₆ H ₄ 2-0CH ₃ -C6H ₄ 3-0CH ₃ -C ₆ H ₄ -C ₆ H _{4 3} 4-0CH 2-phenoxy-C _6Hi, 3-phenoxy-C ₆ H ₄ 4-phenoxv-C ₆ H ₄

-CH ₂ -CH ₂ -

-CH ₂ -CH ₂ -

-CH ₂ -CH ₂ -

-CH ₂ -CH ₂ -

-CH ₂ -CH ₂ -

-CH = CH-

-CH = CH-

-CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH- -CH = CH-

-CH = CH- -CH = CH-

-CH = CH- -CH = CH-

-CH = CH- - (CH ₂ I ₃ -

E R E E S E

E N G E R E S E R E S E S E

E E

E E

3, 67 (s.3H); 6.44 (d, 1H);

8.09 (d.1H).

3.76 (s, 3H) 7.33 (m.o ^< -t)

5.19 (s, 2H); 7.60 (s.1H);

Oei

Oei

OeI OeI

No. R ³

200 C ₆ H ₅

201 C ₆ H ₅

202 C ₆ H ₅

203 2-Cl-C ₆ H;

204 4-Cl-C ₆ H;

205 2-0CH ₃ -C ₆ H ₄

206 4-OCH ₃ -C ₅ H;

207 ^ tC ₄ H ₉ -C ₆ H ₄ 206 C ₆ H ₅

209 C ₆ H ₅

210 211 212 213 214 215 21S 217 2! 8 219 220 221 222

2-Cl-C ₆ H ₄ ^ -Cl-C ₆ H ₄ 2-0CH ₃ -C ₆ H ₄

e ₄ 4 -CH ₃ -C ₆ Ht

C ₆ H ₅ 2 -CH ₃ -C ₆ H ₄

2-Cl-C ₆ H ₄ 4-Cl-C ₆ H ₄

X) _n configuration CH (CH ₃ J-CH ₂ -CH ₂ - e CH ₂ -CH (CH 3) -CH ₂ - e CH ₂ -CH ₂ -CH (CH ₃ ) - e (CH ₂ I ₃ - e (CH ₂ J ₃ - e (CH ₂ J ₃ - e (CH ₂ J ₃ - e (CH ₂ ) 3- e CH = CH-CK ₂ - e

¹ H-NMR

Mp ( ⁰ C)

- (CH ₂ U-

(CH ₂ J ₄ - e (CH ₂ J ₄ - e (CH ₂ ) 4- e (CH2U- e (CH2> 4- e (CH ₂ J ₄ - e (CH ₂ J ₄ - e CH2-CH2-CH (CH3) -CH2- e (CH2J5- e (CH2) 5- e (CH2) 5- e (CH ₂ J ₅ - e (CH ₂ J ₅ - e

3.28 (d, 2H) 3.83 (s.3H) 5.33 (m, 1H) 7.33 (m, 9H) 1.65 (m.4H) 2.60 (t.2H) 3.70 (s, 3H) 7.29 (m <r ,,;

3.73is.3H) 5.17 (s, 2H) 6.52 (0.1H) 7.62 (s.1H) 2.35 (t.2H5 3.65 (s.3H) 5.03 (p.2H) 7.53 (s.IH ).

Oei

Oei

Oei

Oei

configuration

1H-NMR

Mp ( ⁰ C)

2-0CH ₃ -C ₆ H _{4 4} -OCH ₃ -C ₆ H ₄

C6H5

C ₆ H ₅

- (CH ₂ J ₅ -

- (CH ₂ J ₅ - - (CH ₂ J ₅ - -CH ₂ -CH ₂ -CH ₂ -CH (CH 3) -CH ₂ -

E E E

-CH ₂ -CH (CH 3) -CH ₂ -CH (CH 3) -CH ₂ - -CH ₂ -CH (CH ₃ J-CH ₂ -CH (CH ₃₎ -CH ₂₎ -

229 CeH ₅ - (CH2J6- 230 ^C 6H ₅ - (CH2> 4-CH (CH3) -CH2- 231 C ₆ H ₅ -O- -CH2- 232 2-Cl-C ₆ H ₄ -O- -CH ₂ - 233 3-Cl-C ₆ H ₄ -O- -CH ₂ - 234 4-Cl-C ₆ HA-O- -CH2- 235 2,4-Cl ₂ . _C6H3 _ ₀ _ -CH2- 236 2-CH ₃ -C ₆ H ₄ -O- -CH ₂ - 237 4-CH ₃ -C ₆ H ₄ -O- -CH ₂ - 238 2-0CH ₃ -C ₆ H ₄ -O- -CH ₂ - 239 4-OCH ₃ -C ₆ H ₄ -O- -CH ₂ - 240 4-CF ₃ -C ₆ H ₄ -O- -CH ₂ -

E N G E R E S E S E

0.95 (d, 3H) '. , 37 (m.1H) 2.00 (m, 1H) 2.32 (m, 1H) 3.67 (s, 3H) 5.03 (s, 2H) 7.56 (s, H).

1.25 (m, IH) 1.63 (m, 2H) 2.13 (m, 1H) 2.57 (m, 2H) 3.75 (s, 3H) 7.29 (m, 9H)

0.B3, 0.88, 0.96 (3d, 6H) 1.19 (m, 2H); 1,3Ks.9H); 1.79 (m.1H) 2.60 (m, IH) 3.81 (p.3H)

2, 20 (irt, 4H); 3.69 (s.3H); 5.03 (s, 2H);

7.25 (m, 8H); 7.57 (s, 1H).

Oei

Oei

BASF Aktiengesellschaft

8704.96 O.Z. 0050/3949)

Uf Lt UJ UJUJUJIJJJJ UJ UJ IiJ UR UJ UJUJUIUJUJ UY UI UJ UJ

C -

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- · - · - -.-.-. ........ -fyjfvjCMCMPJCVJCMCM CM

PJ PJ PJ PJ PJ PJ PJ PJPJPJ PJPJPJ PJPJCMCM

270 C ₆ H ₅ -O- 271 ^c 6H ₅ -0- 272 2-Cl-C ₆ H ₄ -O- 273 4-Cl-C ₆ H ₄ -O- 274 2.4-Cl ₂ -C ₆ Hs-O 275 2.6-Cl ₂ -C ₆ H ₃ -O 276 2 "CH ₃ -C ₆ H ₄ -O- 277 4-CH ₃ -C ₆ H ₄ -O- 278 ^C 6H ₅ -0- 279 C ₆ H ₅ -O- 280 3-Cl-C ₆ H ₄ -O- 281 C ₆ H ₅ -O- 282 C ₆ H ₅ -O- 283 3-Cl-C ₆ H ₅ -O- 284 C ₆ H ₅ -O- 285 A 1 *)

286 A 2 *)

3 *)

(X) _n * configuration e -CH ₂ -CH (CH 3) -CH ₂ - e - (CH ₂ J ₄ - 'E - (CH ₂ J ₄ - e - (CH ₂ J ₄ - e - (CH ₂ J ₄ - e - (CH ₂ J ₄ - e - (CH ₂ J ₄ - e - (CH ₂ J ₄ - e -CH ₂ -CH ₂ -CH (CH 3) -CH ₂ - e (CH ₂ ) S- e (CH ₂ ) S- e (CH ₂ ) 3-CH (CH 3) -CH 2 - e (CH 2) 6 e (CH 2) 6 e (CH2) 4-CH (CH3) -CH2- e

¹ H-NMR mp ( ⁰ C)

1.88 (m.4H); 2:45 (t, 2H); 3.74 (s, 3H); OeI 3.88 (s.3H); 4, Oct, 2H); 5:09 (s, 2H); 7.18 (m, 9H); 7.64 (s, IH).

1.13. 1.18, 1.25, 1.30Us.6K); 1.73 OeI (p.6H); 1.88, 2.08 (2m, 1HJ; 3.70 (p.3H); 3.82 (s, 3H); 4.90, 5.45 (2m, 1H); 5.05 (m.2H); 7.38 (m, 4H); 7.62 (s 1 H).

1.88, 1.23, 1.27, 1.30Us.6H); 1.13.1.88 OeI (2d.1H); 2.03. 2.27 (2m.IH); 3.70

(s, _3H;; 3.82 (s.3HJ; 5:03 (m.2H); 5.62, 6.30 (2d, 1H), 7:35 (m, 4H), 7.70 (s, 1H).

1.19, 1.24. 1.28, 1.31Us.6H); 1.68, 1.88 OeI (2d, IH); 1 .96, 2.19 (2m, 1H); 3.72 (s, 3H); 3.83 (s, 3H); 5:04 (m.2H);

cn 's!

(X) ₁

Konfigi.ration

Ih-NMR

Mp ( ⁰ C)

A

A 5 *)

290 A 6 *) 291 A 7 *) 292 A 8th*) 293 A 9 *) 29 '. A 10 *) 295 A 11 *) 296 A 12 *) 297 A 13 *) 298 A 14 *) 299 A 15 *) 300 2  furyl 301 N-pyrrolyl

-CH = CH-CH (ISO-C ₃ H ₇ )

302 4-th <: - 8utyl-C ₆ H 4 -CH 2 -c (CH 3) = CH-CH = CH-

EE E E

EE E R E S E

6.16, 6.81 (2d.1H); 7:32 (m, 4H); 7.60 (s.1H).

1.24, 1.29, 1.32, 1.35Us.6H); 1.79 2.00 (2d.1H); 2.17. . 2:44 (2m, IH); 3.71 (S, 3H); 3.83 (s.3H); 5.07 (m, 2H); 6.16, 6.97 (2d.1H); 7:36 (m.4H); 7.60 (s, 1H).

1:45. 1:49 (2s.6H); 2.13 (s, 1H); 3.73 (s.3H); 3.84 (s, 3H); 5:09 (s, 2H); 7,3S (m, 4H); 7.60 (s, 1H).

Oei

Oei

0.77 (d, 3H) 2.42 (sept 3.80 (s, 3ri) 5.03 (s.2H) 6.83 (m.2H) 7.58 (S.IH) 1.33 (s, 9H) 3.72 (s, 3H)

0.98 (d, 3H) 1H); 3.69 (s 4.18 (d.1H) 6.20 (m, 2H) 7.31 (m, 4H)

2.22 (s.3H) 3.87 (s.3H)

OeI OeI

3H);

3.43 (s, 2H) 5.13 (s.2H)

Oei

No. R ³

(X) ₁

configuration

¹ H-NMR

Mp ( ⁰ C)

305 H 306 H 307 H 308 H 309 H 354 H 355 H 356 1-methylcyclohexyl 357 4-Cl-C ₆ H ₄ 358 4-Cl-C ₆ H ₄ 359 ^C 6H ₅ 360 ι -Methylcyclopropyl

2-methylcyclopropyl

-CH ₂ -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) - -CH ₂ -CH (CH ₃ ) -CH ₂ -CH (CH ₂ H ₅ ) -

-CH ₂ -CH (CH ₃ J-CH ₂ -CH (nC ₃ H ₇ ) -

-CH ₂ -CH (CH ₃ J-CH ₂ -CH ₂ -CH (iC ₃ H ₇ )

-CH ₂ -C (CH ₃ J ₂ -CH ₂ -CH (CH ₃ J-CH ₂ -

- (CH ₂ J ₅ -CH (C ₂ H ₅ ) -

(CH ₂ ) ₅ -CH (nC ₃ -H ₇ J-

-CH ₂ -O-CH ₂ -C (CH ₃ J ₂ -

- (CH ₂ ) ₄ -O-CH ₂ -C (CH ₃ ) 2-

-CHCl-

-C (CH3) 2-

-CH = CH- (CH ₂ );

5.88 (d.1H); 6.10 (m, 1H); 6.45 (d, 1H); 7:35 (m.8H); 7.63 (s.1H).

1-methyl-2,2-dichlorocyclopropyl 2-phenyl-cyclopropyl

e 0.89 (m.9H); 1.25 (m.1H); Oei ΓΟ e 1:59 (m, 4H); 2.4Km ₁ IH); CJ 3.7Ks.3H); 3.64 (s.3H); 5:03 (s.2H); 7:36 (m, 4H); 7.SS (S.1H). Oei e Oei e Oei ro e VJ e • few e Oei cn e Oei cn e Oei vi e Oei e Oei e Oei e 0.65 (m, 2H); 1.22 (m, 2H); Oei e 1.30 (s.3H); 3.70 (s, 3H); 3.83 (s, 3H); 5.00 (p.2H); 7:14 to 7:48 (Pi ι.4H); 7.60 (s.IH). Oei e Oei e Oei e Oei e

(X) ₁

configuration

¹ H-NMR

Mp ( ⁰ C)

1-phenylcyclopropyl

1- (2'-chlorophenyl-cyclopropyl

-Chlorophenyl) -cyclopropyl-chlorophenyl-cyclopropyl, 4'-dichlorophenyl) -cyclopropyl, 6'-dichlorophenyl-cyclopropyl, 4'-dichlorophenyl) -cyclopropyl-fluorophenyl) -cyclopropyl-fluorophenyl) -cyclopropyl-fluorophenyl) -cyclopropyl-8-romphenyl) -cyclopropyl-methylphenyl) -cyclopropyl-methylphenyl) -cyclopropyl-methylphenyl) -cyclopropyl 4'-oxymethylphenyl-cyclopropyl-tert-butylphenyl) -cyclopropyl-Trif J.uomethylphenyl) -cyclopropyl-methoxyphenyl) -cyclopropyl-methoxyphenyl) -cyclopropyl-methoxyphenyl ) -cyclopropyl, 4'-oxethoxyphenyl) -cyclopropyl .6'-dimethoxyphenyl) -cyclopropyl, 4'-oxymethoxyphenyl) -cyclopropyl 1- (3'-r-dimethcyvphenvl-cvclopropvl

367 1- (3 * 366 1- (4 * 369 1- (2 ' 370 1- (2 ' 371 1- (3 ' 372 1- (2 ' 373 1- (3 ' 37 * 1- (4 ' 375 i - (· 376 1- (2 ' 377 1- (3 ^f 378 1- (4 * 379 1- (3 ' 380 1- (4 ' 381 1- (3 · 382 1- (2 · 383 1- (3 ' 384 1-U " 385 1- (2 ' 386 1- (2 * 387 1- (3 '

E N G E E R E S E R E S T E R E S

1.21 (m.2H); 1.76 (m.2H); 3.68 (s, 3H); 3.77 (s, 3H); 5.00 (s.2H); 7.08-7.40 (m.8H); 7:55 (s.1H).

106-106 100-101

OeI OeI

84-85

* 'Formulas see previous text

The reported NMR rates indicate the chemical shift Ιδ) of the protons in ppm relative to tetramethylsilane. The solvent used is COCl ₃ .

r 3 - (X) -CO-CH ₂ - <(

Table 2: Compounds of the formula I configuration

Mp ( ⁰ C)

310 OCH ₃ CN H - (CH ₂ U-CH (CH ₃ J-CH ₂ 311 OCH ₃ CN CeH ₅ - (CH ₂ ) ₃ -CH (CH ₃ ) -CH ₂ 312 OCH ₃ CN A ₂ *) - 313 OCH ₃ CONH ₂ H - (CH ₂ ) ^ - CH (CH ₃ J-CH ₂ 3U OCH ₃ CONK ₂ C ₆ H ₅ "(CH ₂ ) ₃ -CH (CH ₃ ) -CH ₂ 315 OCH ₃ CONH ₂ A ₂ *) - 316 SCH ₃ CO ₂ CH ₃ H - (CH ₂ ); - CK (CH 3) -CH 2 317 SCH ₃ CO2CH3 C6H5 - (CH2) 3-CH (CH3) -CH2- 316 SCH ₃ C02CH3 A ₂ *) - 319 SCH ₃ CN H - (CH ₂ U-CK (CH 3i-CH ₂ 320 SCH ₃ CN C6H ₅ - (CH ₂ ) 3 -CH (CH 3) -CH ₂ 321 SCH ₃ CN A ₂ *) - 322 SCH ₃ CONH ₂ H - (CH ₂ i4-CH (CH 3) -CH ₂ 323 SCH ₃ CONH2 C _6: =: - (CH ₂ ) 3 -CH (CH 3) -CH ₂ 324 SCH ₃ C0NH2 A ₂ *) - 325 Cl C0 ₂ CH3 H - (CH2K-CH (CH 3) -CH 2 326 Cl CO ₂ CH ₃ C ₆ H ₅ - (CH2) 3-CH (CH3) -CH2- 327 Cl CO ₂ CH ₃ A ₂ *) - 328 Cl CN H - (CH ₂ ); - CH (CH ₃ ) -CH ₂ 329 Cl CN C ₆ H ₅ -JCH ₂ J ₃ -CH (CH ₃ J-CH ₂ 330 Cl CN A ₂ *) - 331 Cl CONH ₂ H - (CH2) 4-CH (CH3) -CH2-

E / Z

EE E E

Oei

Konigigi ti.on

332 Cl CONH ₂ C ₆ H ₅ - (CH ₂ J ₃ -CH (CH ₃ J-CH ₂ 1-methylcyclopropyl 333 Cl CONH ₂ A ₂ * ' - 334 N (CH ₃ J ₂ CO ₂ CH ₃ H - (CH ₂ J ₄ -CH (CH ₃ J-CH ₂ 335 N (CH ₃ J ₂ CO ₂ CH ₃ C6H5 - (CH ₂ J ₃ -CH (CH ₃ J-CH ₂ 336 N (CH ₃ J ₂ CO ₂ CH ₃ A ₂ *) - 337 N (CH ₃ I ₂ CN H - (CH ₂ J ₄ -CH (CH ₃ J-Ch ₂ 338 N (CH ₃ J ₂ CN C ₆ H ₅ - (CH ₂ J ₃ -CH (CH ₃ J-CH ₂ 339 N (CH ₃ J ₂ CN A ₂ *) - 340 N (CH ₃ J ₂ CONH ₂ H - (CH ₂ J ₄ -CH (CH ₃ J-CH ₂ 341 N (CH _: ' ₂ CONH ₂ C ₆ H ₅ - (CH ₂ J ₃ -CH (CH ₃ J-CH ₂ 342 N (CH ₃ J ₂ CONH ₂ A2 *) - 343 NHCH ₃ CO ₂ CH ₃ H -CH 2) 4-CH (CH3) -CH2- 344 NHCH ₃ CO ₂ CH ₃ C ₆ H ₅ -CH ₂ J ₄ -CH (CH ₃ J-CH ₂ - 345 NHCH ₃ CO ₂ CH ₃ A ₂ *) - 346 NHCH ₃ CN H -CH ₂ J ₄ -CH (CH ₃ J-CH ₂ - 347 NHCH ₃ CN CeH ₅ -CH 2) 4-CH (CH ₃₎ -CH 2 348 NHCH ₃ CN A ₂ *) - 349 NHCH ₃ C0NH2 H -CH 2) 4-CH (CH3) -CH2- 350 NHCH ₃ CONH ₂ CeH ₅ -CH 2) 3-CH (CH3) -CH2- 351 NHCH ₃ CONH2 A ₂ *) - 352 OCH ₃ CN 2-'- C ₆ H ₄ - 353 OCH ₃ CN

E / 2

E / Z

64-65 OeI

* Formula see previous text

27

2745S7

The new compounds, generally printed, are characterized by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes and Basidiomycetes. They are sometimes systemically effective and can be used as foliar and soil fungicides.

Particularly interesting are the fungicidal compounds for combating a variety of fungi on various crops or their seeds, especially wheat, rye, barley, oats, rice, corn, turf, cotton, soybeans, coffee, sugarcane, horticultural and ornamental plants, viticulture as well as vegetables - such as cucumbers, beans and pumpkin plants -.

The new compounds are particularly suitable for controlling the following

Plant diseases: 15

Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits, Podosphaera leucotricha on apples,

Uncinula necator on vines, 20 Puccinia species on cereals,

Rhizoctonia species on cotton and turf, Ustilago species on cereals and sugarcane, Venturia inaequalis (scab) on apples,

Helminthosporium species on cereals, 25 Septoria nodorum on wheat,

Botiytis cinerea (gray mold) on strawberries, vines, Cercospoia arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley,

Pyricularia oryzae on rice, 30 Phytophthora infestans on potatoes and tomatoes,

Fusarium and Verticillium species on different plants,

Plasmopara viticola on vines, • Alternaria species on vegetables and fruits.

All compounds are applied by spraying or dusting the plants with the active ingredients or by treating the seeds of the plants with the active ingredients. The application is carried out before or after the infection of the plants or seeds by the fungi.

The new substances can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend entirely on the intended use, they should in any case ensure a fine and uniform distribution of the active substance. The formulations are in

known manner, e.g. by stretching the active ingredient with solvents and / or excipients, optionally with the use of emulsifiers and dispersing agents, it also being possible to use other organic solvents as auxiliary solvents in the case of using water as diluent. Suitable auxiliaries are essentially: solvents such as aromatics (eg xylene), chlorinated aromatics (eg chlorobenzene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol), ketones (eg cyclohexanone), amines (eg ethanolamine, dimethylformamide ) and water; Carriers like natural

IQ minerals (eg kaolins, clays, talc, chalk) unc, ground synthetic minerals (eg highly disperse silicic acid, silicates); Emulsifiers, such as nonionic and anionic emulsifiers (for example polyoxyethylene-fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants, such as lignin, liquors and methylcellulose.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt. I of active ingredient.

Depending on the nature of the desired effect, these application rates are between 0.02 and 3 kg of active ingredient or more per ha. The novel compounds can also be used in the protection of materials, e.g. against Paecilomyces variotii.

The agents or the ready-to-use preparations prepared therefrom, such as solutions, emulsions, suspensions, powders, dusts. Pastes or granules are applied in a known manner, for example by spraying, atomizing, dusting, scattering, pickling or pouring.

Examples of such preparations are:

I. 90 parts by weight of compound no. 34 is mixed with 10 parts by weight of N-methyl-a-pyrrolidone and obtains a solution which is suitable for use in the form of very small drops.

II. 20 parts by weight of compound no. 226 are in a mixture

dissolved, consisting of 80 parts by weight of xylene, 10 parts by weight of

> Addition product of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonic acid and 5 parts by weight of the adduct and 40 moles of ethylene oxide to 1 mole of castor oil.

By pouring and finely distributing the solution in water to obtain an aqueous dispersion.

ΙΠ. 20 parts by weight of compound no. 286 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring and finely distributing the solution in water to obtain an aqueous dispersion.

IV. 20 parts by weight of compound no. 289 are in a mixture

dissolved, which consists of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280 ⁰ C and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in water to obtain an aqueous dispersion.

V. 80 parts by weight of compound no. 34 are well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite liquor and 7 parts by weight of powdered silica gel and mow in a hammer mill. By fine

Distributing the mixture in water gives a SpritzbrC'he. VI. 3 parts by weight of compound no. 226 are used with 97 parts by weight

finely divided kaolin intimately mixed. Obtained in this way a dust, the 3 Gew./. of the active ingredient. 25

VII. 30 parts by weight of compound no. 286 are mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil. which has been sprayed onto the surface of this silica gel, intimately mixed. This gives a preparation of the active substance with good adhesion.

VIII. 40 parts by weight of compound no. 289 are intimately mixed with 10 parts by weight of sodium salt of phenolsulfonic acid-ha-formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water. A stable aqueous dispersion is obtained. Dilution with water gives an aqueous dispersion.

IX. 20 parts by weight of compound no. 34 are mixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol

polyglycol ether, 2 parts by weight of sodium salt of a phenolsulfone

acid-urea-formaldehyde condensate and 68 parts by weight of a

irrigated paraffinic mineral oil, rian receives a stable oily dispersion.

30

274SS7

The agents according to the invention may also be present together with other active substances in these application forms, e.g. Herbicides, insecticides, growth regulators and fungicides, or even mixed with fertilizers and applied. In the case of mixing with fungicides, in many cases enlargement of the fungicidal activity spectrum is obtained.

The following list of fungicides with which the novel compounds may be combined is intended to illustrate the possible combinations 10, but not to limit it.

Fungicides which can be combined with the compounds according to the invention are, for example:

Sulfur,

Dithiocarbamates and their derivatives, such as Ferridimethyldithiocarbamat, zinc dimethyldithiocarbamate,

Zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate,

Manganese zinc ethylenediamine-bii-dithiocarbamate, Tetramethylthiuramdisulfide, Ammonia complex of zinc (N.N-ethylene-bis-dithiocarbamate),

Ammonia complex of zinc (N ₁ N'-propylene-bis-dithiocarbamate), zinc (N ₁ N'-propylene-bis-dithiocarbamate),

N ₁ N ¹ polypropylene bis (thiocarbamoyl) disulfide; Nitroderivate, like

Dinitro (1-methylheptyl-phenyl-crotonate, 2-heptyl-4,6-dinitrophenyl-3,3-dimethyl-acrylate, 2-sec-butyl-4,6-dinitrophenyl-isopropylcarbonate; 5-nitro-isophthalic diisopropyl ester

heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl-phthalimidophosphonothioate, 5-amino-1- [bis ( dimethylamine) -phosphinyl] -3-phenyl-1,2,4-triazole, 2,3-dicyano-i.4-dithioanthraquinone, 2-T5.1O-1,3-dithio (4,5-b) - quinoxaline, ethyl 1 - (butylcarbamcyl) -2-benzimidazole-carbamate, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidzole, 2- (thiazolyl- (4)) -benzimidzole,

31

274SS7

N- (I ₁ I, 2,2-tetrachloroethylthio) -tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthio-phthalimide,

5 N-dichlorofluoromethylthio-N ¹ , N ¹ -dimethyl-N-phenyl-sulfuric acid diamide,

5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-Rhodanemethylthiobenzothiazole,

1,4-dichloro-2,5-dimethoxybenzene, 4-U-chlorophenylhydroazanol-S-methyl-S-isoxazolone, pyridine-2-thio-i-oxide,

8-hydroxyquinoline or its copper salt, 2, S-dihydro-S-carboxanilido-G-methyl-1,4-oxathiin, 2.S-dihydro-S-carboxanilido-B-methyl-i 4-oxathiin-4,4 -dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxylic acid aniline, 2-methyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2, 4,5-Trimethyl-furan-3-carboxylic acid anilide, 2.S-dimethyl-furan-S-carboxylic acid cyclohexylamide, N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide, 2-methyl-benzoic acid anilide,

2-iodo-benzoic acid anilide,

N-formyl-N-morpholine-2,2,2-trichlorethylacetal, Piperazine-1,4-diylbis- {1- (2,2,2-trichloro-ethyl) -formamide,

1- {3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroeth, 2,6-dimethyl-N-tridecyl-morpholine or its salts, 2, B-dimethyl-N-cyclodedecyl-morpholine or its salts,

N- [3- (p-tert-butylphenyl) -2-methylpropyl] -cis-2,6-dimethylmorpholine, N- [3- (p-tert-butylphenyl)] 2-methylpropyl] piperidine,

1- [2- (2,4-0ichlorphenyl) -4-ethyl-1,3-dioxolan-2-yl-ethyl] -1H-1, 2,4-TRIA 30 2oi

1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-

triazole, 'N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazol-yl-urea,

1- {4-chlorophenoxy) -3,3-dimethyl-1- (IH-I, 2,4-triazol-1-yl) -2-butanone, 35 1- (4-chlorophenoxy) -3,3-dimethyl -1- (1H-1,2,4-triazol-1-yl) -2-butanol,

α- (2-chlorophenyl) -a- (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethylamine-4-hydroxy-6-methyl / pyrimidine,

Bis (p-chlorphenyll-S-pyridinemethanol,

1, 2-bis- {3-ethoxycarbonyl-2-thioureido) benzene, 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene,

32

and various fungicides, such as dodecylguanidine acetate,

3-ΠΜ3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] -glutarimide, hexachlorobenzene, OL-methyl-N- (2,6-dimethylphenyl) -N-furoylf2) -alaninate, DL-N (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl-D ₁ L-2-aminobutyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine, 3- [3 , 5-Oichlorphenyl (-5-methyl-5-methoxymethyl] -1,3-oxazolidine-2,4-dione,

10 3- (3, S-OichlorophenyD-i-isopropylcarbamoylhydantoin,

N- (3,5-dichlorophenyl-1, 2-dimethylcyclopropane-1,2-dicarboximide, -cyano- [N- (ethylaminocarbonyl) -2-methoxy-imino] -acetamide, 1- [2- (2,4 -0-chlorophenyl) -pentyl] -1H-1,2,4-triazole, 2,4-fluoro-'- (IH-1,2,4-triazolyl-1-methyl) -benzhydryl alcohol, N- (3-chloro) 2,6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1 - ((bis (4-fluorophenyl) -methylsilyl) -methyl) -IH-I.2, 4-triazole.

Application example

As comparative active compounds, N-tridecyl-2,6-dimethylmorpholine (A) and α- (2-benzoyloxyphenyl) - / J-methoxyacrylic acid ester (B) - known from DE 1 164 152 and from EP 17B 826 - were used.

25 Application Example 1

Efficacy against wheat brown rust

Leaves of potted wheat seedlings of the variety "Frühgold" were dusted with spores of the brown rust (Puccinia recondita). Thereafter, the pots were placed for 24 hours at 20 to 22 ⁰ C in a high humidity chamber (90 to 95 7.). During this time the spores sprouted and the germ tubes penetrated the leaf tissue. The infected plants were then sprayed to runoff with aqueous liquors containing 80 I of active ingredient and 20 "/. Emulsifier in the dry substance. After drying the spray coating, the test plants were in the greenhouse at temperatures between 20 and 22 ⁰ C and 65 to 70 7 After 8 days, the extent of rust fungus development on the leaves was determined.

The result shows that the active ingredients 34, 192, 226, 286, 287, 289, 360, 361, 362, 363, 368 and 369 are better fungicidal when applied as 0.025% (w / v) spray liquors Show effect (90 '/.) Than the known comparison active compounds A and B (50 7.).

33

274SS7

Application Example 2 Activity against Pyrenophora teres

Barley seedlings of the "igri" variety were sprayed to drip point in the two-leaf stage with aqueous suspensions containing 80% active ingredient and 20% emulsifier in the dry matter. After 24 hours, the plants were inoculated with a spore suspension of the fungus Pyrenophora teres and placed for 48 hours in a climatic chamber with high humidity at 18 ⁰ C. The plants in the greenhouse at 20 were - cultured 22 ⁰ C and 70 7. RH for an additional 5 days. Then the extent of symptom development was determined.

The result shows that the active ingredients I ₁ 4, 11. 28, 34, 35, 71, 73, 83,

98, 101, 109, 154, 169, 192, 226, 271, 285, 286, 287, 288, 289, 304, 306,

355, 360, 361, 363 and 368 when used as 0.05 Hg spray

a better fungicidal action (90 7.) show than the known comparison drug A (50 Z).

20 Application Example 3

Efficacy against Plasnopara viticola

Leaves of pot fry of the variety "Müller Thurgau" were sprayed with aqueous spray mixture containing 80 7. active ingredient and 20 7. emulsifier in the dry matter. In order to be able to assess the duration of action of the active ingredients, the plants were placed in the greenhouse for 8 days after the spray coating had dried on. Only then were the leaves infected with a zoospore suspension of Plasmopara viticola (vine peronospora). Thereafter, the vines were first set up for 48 hours in a water vapor-saturated chamber at 24 ⁰ C and then for 5 days in a greenhouse with temperatures between 20 and 30 ⁰ C. After this time, the plants were again placed in the humid chamber for 16 hours to accelerate the sporangium support outbreak. Then, the extent of the mushroom outbreak was evaluated on the undersides of the leaves.

The result shows that the active ingredients 4, 11, 23, 28, 32, 34, 35, 71, 73, 79, 81, 82, 83, 98, 101, 109, 154, 161, 169, 179, 192, 226 , 271, 285, 286, 287, 288, 289, 304, 356, 357, 359, 360, 362, 363, 364, 368 and 369 have a better fungicidal action (when used as a spray liquid 7.ige 0.05 90 I ) show as the known comparison active substance A (50 7.).

Claims (3)

Erfindungsan talks 1. Fungicidal agent, characterized by a content of a solid or liquid carrier and a fungicidally effective amount of a compound of formula I. R ³ - (X) -CO-CH ₂ η R 2 in which R ¹ denotes C ¹ -C 4 -alkoxy, C 1 -C 4 -alkylthio, halogen or optionally mono- or disubstituted by C 1 -C 18 -alkyl, R ² denotes C 1 -C 4 -alkoxycarbonyl, cyano or the group CONH ₂ , R ^{3 is} hydrogen, halogen, cyano, aryl, aryloxy, wherein the aromatic ring is optionally substituted by a. More than one of the following radicals is substituted: C ₁ -C 6 -alkyl, C ₁ -C ₄ -alkenyl, C ₁ -C ₂ -haloalkyl, C ₁ -C ₁ -alkoxy, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ - alkyl. Aryl, arylC ^ C ^ alkyl, aryloxy, aryloxy-Ci-Cij-alkyl, aryloxy-Ci-C ^ alkoxy, haloaryloxy-Ci-C / j-alkoxy, halogen, halo-Ci-C ^ alkoxy, Ci-C ^ -alkylthio, thiocyanato, cyano, nitro, or R ^{3 is} a saturated or unsaturated heterocyclic radical, Ca-Cy-cycloalkyl, Cs-C6-cycloalkenyl, adamantyl, fluorenyl or a substituted cyclopropyl radical which is substituted by methyl, halogen, Ci-C ₂ haloalkyl, Ca-Cij-alkenyl, C ₂ -C, -haloalkenyl, methoxycarbonyl-Ca-C, -alkenyl, cyclopentylidenemethyl, phenyl, halophenyl, C ₂ alkoxyphenyl, Ci-C / f alkylphenyl, X is an optionally unsaturated by halogen or hydroxy, optionally unsaturated Ci-Ci ₂ -Alky. ¹ enrest means and η is the number 0 or 1. 30 2. A process for the preparation of a fungicidal agent, characterized in that a fungicidally effective amount of an ortho-substituted carboxylic acid benzyl ester of the general formula, R ³ - (X) -CO- CH in which R 'is C 1 -C 4 -alkoxy, C 1 -C 6 -alkylthio, halogen or, if appropriate, C 1 -C 4 -alkyl or monosubstituted or disubstituted amino, R ^{2 represents} C 1 -C 4 -alkoxycarbonyl, cyano or the group CONH 2, R ^{3 is} hydrogen, halogen, cyano, aryl, aryloxy, where the aromatic ring is optionally substituted by one or more of the following radicals: C 1 -C 6 -alkyl, C 2 -C 4 -alkenyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkyl, Alkoxy, Ci-Ct-alkoxy-Ci-C ^ -alkyl, aryl, aryl-Ci-C2-alkyl, aryloxy, aryloxy-Ci-Ci, -alkyl, aryloxy-Ci-C ^ -alkoxy, haloaryloxy-Ci-C C 1 -C 4 -alkoxy, halogen, halogeno-C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, thiocyanates cyano, nitro, or R ³ denotes a saturated or unsaturated heterocyclic radical, C 3 -C 7 -cycloalkyl, C 3 -C 5 -cycloalkenyl, adamantyl, Fluorenyl or a substituted cyclopropyl radical which is substituted by methyl, halogen, Ci-C2-haloalkyl, Ca-Cif-alkenyl, C2-Ci _t haloalkenyl, methoxy carbonyl-CaC / j-alkenyl, cyclopentylidenemethyl, phenyl, halophenyl, C1-C2-alkoxyphenyl, Ci-C ^ -alkylphenyl, X is an optionally substituted by halogen or hydroxy, optionally unsaturated Ci-C ^ -Alkylenrest means and η is the number 0 or 1, mixed with a solid or liquid carrier. 30 3. Use of an ortho-substituted carboxylic acid benzyl ester of the general formula in which R ^{1 is} C ₁ -C 6 -alkoxy, C ₁ -C 4 -alkylthio, halogen or, if appropriate, C ₁ -C 4 -alkyl-substituted or disubstituted amino, R ^{2 is} Ci-Cij-alkoxycarbonyl, cyano or the group CONH2, R ³ is hydrogen, halogen, cyano, aryl, aryloxy wherein the aromatic ring is optionally substituted by one or more of the following residues is substituted: Ci-C6-alkyl, C2-C £ _t alkenyl, Ci-C2-haloalkyl, Ci-C6 Alkoxy, Ci-Cij-alkoxy-Ci-Cif-alkyl, aryl, aryl-Ci-C2-alkyl, aryloxy, aryloxy-Ci-Cif-alkyl, aryloxy-Ci-Ctf-alkoxy, haloaryloxy-Cj-Cif-alkoxy , Halogen, halogeno-C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, thiocyanato, cyano, nitro, or R ^{3 is} a saturated or unsaturated heterocyclic radical, C 3 -C 7 -cycloalkyl, C 6 -C 6 -cycloalkenyl, adamantyl, fluorenyl or a substituted cyclopropyl means which is substituted by methyl, halogen, Ci-C2-haloalkyl, C3Cif-alkenyl, C2-Ci _f -haloalkenyl, methoxycarbonyl-C3Cif-Alk3nyl, cyclopentylidenemethyl, phenyl, halophenyl, C1-C2 alkoxy phenyl, Ci-Ctj-alkylphinyl, X is an optionally substituted by halogen or hydroxy, optionally unsaturated Ci-Ci2-alkylene radical and η is the number 0 or 1, to combat fungi.
30 274SS7 Method of combating fungi, characterized in that the fungi or the materials, plants, seeds or soil threatened by fungal attack are treated with a fungicidally effective amount of a compound of the formula R ³ - (X) -CO-CH ₂ η R 2 in which R ¹ denotes C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, halogen or optionally mono- or disubstituted by C 1 -C 1 -alkyl, means amino, R ^{2 is} C 1 -C 4 -alkoxy-carbonyl, cyano or the group CONH 2, R ^{3 is} hydrogen, halogen, cyano, aryl, aryloxy, where the aromatic ring is optionally substituted by one or more of the following radicals: C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl. C 1 -4 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 8 -alkoxy-C 1 -C 6 -alkyl, aryl, aryl-C 1 -C 2 -alkyl, aryloxy, aryloxy-C 1 -C 6 -alkyl, aryloxy-C 1 -C 4 -alkyl C 1 -, alkoxy, haloaryloxy-C 1 -C 4 -alkoxy, halogen, halogeno-C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, thiocyanato, cyano, nitro, or R ³ denotes a saturated or unsaturated heterocyclic radical, C 1 -C 6 -cycloalkyl, C 1 -C 6 -cycloalkenyl, adamantyl, fluorenyl or a substituted cyclopropyl radical which is substituted by methyl, halogen, C 1 -C 2 -haloalkyl, C 3 -C 4 -alkenyl, C 2 -C 4 -haloalkenyl, methoxycarbonyl-carbonyl Ci, alkenyl, cyclopentylidenemethyl, phenyl, halophenyl, Ci-C2-alkoxyphenyl, Ci-C X is an optionally substituted by halogen or hydroxy, optionally unsaturated Ci-Ci2-alkylene radical and η is the number 0 or 1,
treated.